Identifying the Origin of Rock Phosphates and Phosphorus Fertilisers Using
Isotope Ratio Techniques and Heavy Metal Patterns
3498-846-0
Von der Fakultat fur Lebenswissenschaften
der Technischen Universitat Carolo-Wilhelmina
zu Braunschweig
zur Erlangung des Grades eines
Doktors der Naturwissenschaften
(Dr. rer. nat.)
genehmigte
Dissertation
von Mamdoh Sattouf
aus Horns / Syrien
Table of contents
TABLE OF CONTENT
Table of content
i
List of tables
v
List of figures
ix
List of symbols, acronyms and abbreviations
xi
1
Introduction
1
2
Literature review and objectives of this study
7
2.1 Heavy metals in rock phosphates and P-fertilisers
7
2.1.1 Types and world production of rock phosphates
7
2.1.2 Heavy metals in rock phosphates from different origin
8
2.1.3 Transfer of radionuclides and heavy metals from rock phosphates to P-fertilisers
during the production process
10
2.1.4 Effects of heavy metals applied with P-fertilisers on soil-plant-human system
12
2.2 Isotopic fingerprint method (isotopic signature)
16
2.2.1 Definition and types of isotopes
16
2.2.2 Abundance of the isotopes on earth
22
2.2.3 Isotopic fractionation
24
2.2.4 Isotope ratios as a fingerprint to identify the origin of different materials
25
2.3 Objectives of this study
28
3
Material and methods
31
3.1 Selection of samples
31
3.2 Analytical methods of heavy metal determination
33
3.3 Measurements of Sr and U isotopes using Thermal Ionisation Mass Spectrometry
(TIMS)
33
87
86
3.3.1 Measurements of R( Sr/ Sr) in rock phosphates and P-fertilisers by Thermal
Ionisation Mass Spectrometry
34
234 238
235 238
3.3.2 Measurements of R( U/ U)- and R( U/ U) in rock phosphates and Pfertilisers by thermal ionisation mass spectrometry
41
3.5 Calculation and statistical analysis
47
3.5.1 Cluster analysis
•
47
3.5.2 Discriminant function analysis
•
47
3.5.3 Principal components and factor analysis
48
Table of contents
3 5 4 Calculation of isotope ratios in P-fertilisers or rock phosphates m e d to produce
compound fertilisers in order to trace back the origin of P-components in
F
..
49
compound fertilisers
•
*
51
4
Results
•
5
4.1 Phosphorus and microelements in rock phosphates from different origin
*
52
4.2 Heavy metals in rock phosphates and P-fertilisers from different origin
4.3 U concentration in different types of rock phosphates and P-containing fertilisers
56
4.4 Sr concentration in different types of rock phosphates and P-containing fertilisers 63
4.5 Fingerprinting the geographical origin of rock phosphates according to their content of
heavy metals using multivariate statistical analysis
4.5.1 Classification of rock phosphates using discriminant analysis and hierarchical
cluster analysis
••—
4.5.2 Natural relationships among heavy metals in different rock phosphates as
determined by cluster analysis
*
4.5.3 Determination of heavy metal pattern by principal component analysis (PCA)
'5
01
4.6 Sr isotope ratios in rock phosphates and P-containing fertilisers
°
4.6.1 Sr isotope ratio in rock phosphates as a tool to identify their geographical origins 81
83
5.6.2 Transfer of R(87Sr/86Sr) from rock phosphates to P-fertilisers
4.6.3 Natural Sr isotope ratio variation as a tool to trace backs the origin of P-fertilisers
of different manufacturers
,....»„........
^5
4.7 U isotope ratios in rock phosphates and P-containing fertilisers
^2
234 238
4.7.1 Natural R( U/ U) in rock phosphates from different origin and P-fertilisers 92
95
4.7.2 Transfer of R(234U/238U) from rock phosphates to P-fertilisers
4.7.3 Determination of the origin of P-fertilisers of different manufacturers based on
natural R(234U/238U)
97
4.7.4 R(234U/238U) in farmyard manures and organo-mineral fertilisers
4J.5 R(235U/238U) as tool to detect contamination with anthropogenic U
5
Discussion...........
„
„
4
99
°
l0
<##
103
5.1 Fingerprinting the origin of rock phosphates and P-fertilisers by their heavy metal
pattern
«
103
5.1.1 Identifying the origin of rock phosphate to reduce the heavy metals and
radionuclides in P-fertilisers and to avoid environmental pollution,
1° 3
5.1.2 Factors affecting U concentration in rock phosphates and P-containing fertilisers 105
5.13 Heavy metal pattern as indicator to rock phosphate origins
5.1.4 Heavy metal pattern as indicator to the origins of P-fertilisers
1° 7
H°
Table of contents
Hi
5.1.5 Influence of declining quality of rock phosphates on U content in P-fertilisers ... 111
5.2 Use of Sr isotopes to identify the origin of rock phosphates and P-fertilisers
114
5.2.1 Identifying the origin of rock phosphates and P-fertilisers using the Sr isotope ratio
and total Sr concentrations
114
5.2.2 Factors affecting the Sr isotope ratio in rock phosphates
115
5.2.3 Tracing back the origin of P-fertilisers of different manufacturers based on
R(87Sr/86Sr)
117
5.3 Use of U isotopes to identify the origin of rock phosphates and P-fertilisers and as an
indicator of natural or anthropogenic U
120
234 238
5.3.1 Identifying the origin of rock phosphates and P-fertilisers using R( U/ U) and
total U concentrations
121
5.3.2 Tracing back the origin of P-fertilisers of different manufacturers based on
R(234U/238U)
123
235 238
5.3.3 R( U/ U) as an indicator to natural or anthropogenic U
124
5.4 Application of Sr and U isotope ratios together to identify the sources of phosphorus in
compound mineral fertilisers
126
6
Summary/Zusammenfassung.
131
7
References
137
8
Glossary
151
9
Appendix
155